The present invention relates to novel shaped catalysts for heterogeneously catalyzed reactions in the form of hollow cylinders or annular tablets whose end faces are rounded both to the outer edge and to the edge of the central hole, so that they have no right-angled edges
EP-A-184 790 discloses shaped catalysts for heterogeneously catalyzed reactions in the form of a hollow cylinder which have curved xe2x80x9cend facesxe2x80x9d at the outer edge of the cylinder.
WO-A-99/48606 discloses catalysts in the form of annular tablets having dimensions of 5 mmxc3x975 mmxc3x972 mm (height x diameter x diameter of the central hole).
However, these catalysts leave something to be desired. In particular, the pressure drop over a bed of these catalysts is not yet optimal.
It is an object of the present invention to provide shaped catalysts for heterogeneously catalyzed reactions having improved properties, in particular a reduced pressure drop.
We have found that this object is achieved by new and improved catalysts for heterogeneously catalyzed reactions in the form of hollow cylinders or annular tablets whose end faces are rounded both to the outer edge and to the edge of the central hole (FIG. 1).
The catalysts of the present invention are produced by methods known per se, for example by precipitation of the oxides, hydrated oxides, hydroxides or other sparingly soluble compounds of the components from solutions of their salts, or by intensive mixing of the oxidic and/or salt-like starting materials, which may be dissolved and/or suspended in water or organic solvents, subsequent drying and, if appropriate, thermal decomposition of the salts, milling to a suitable tabletable particle size, shaping to the shape according to the present invention in suitable tableting machines and, if appropriate, subsequent thermal treatment at elevated temperatures in an oxidizing, reducing or inert atmosphere. Shaping aids such as graphite, carbon black, stearic acid, starch, polyacrylic acid, mineral oil, vegetable oil, methylcellulose, etc., and also reinforcing materials such as inorganic fibers, for example glass fibers or the like, or inorganic powders, for example metal powders, metal flocs, inert support materials, e.g. SiO2, metal silicates and aluminum silicates, aluminum oxides, aluminum hydroxides, hydrated aluminum oxides, MgO, TiO2, ZrO2, Nb2O3, pumice, silicon carbide and/or magnesium silicates, can be added to the catalyst composition at any point during shaping.
The shaped catalysts of the present invention for heterogeneously catalyzed reactions are in the form of hollow cylinders or annular tablets of catalytically active material or preferably comprise inert support material which has been shaped into hollow cylinders or annular tablets and on which a catalytically active composition has been applied, where the external diameter of the hollow cylinders or annular tablets is from 3 to 20 mm, preferably from 3 to 10 mm, particularly preferably from 3 to 7 mm, in particular from 3.5 to 6.5 mm, with an internal diameter which is from 0.1 to 0.7 times the external diameter, and a length which is from 0.2 to 2 times, preferably from 0.3 to 1.8 times, particularly preferably from 0.4 to 1.6 times, the external diameter, and the radius of curvature of the end faces is from 0.01 to 0.5 times, preferably from 0.05 to 0.4 times, particularly preferably from 0.1 to 0.2 times, the external diameter.
FIG. 1 illustrates a possible cross section of the shaped catalysts of the present invention.
FIG. 2 illustrates a cross section of a shaped catalyst according to the present invention, having dimensions of 5 mmxc3x975mmxc3x972.5 mm (height x diameter x diameter of the central hole) and end faces rounded to the outer edge and to the edge of the central hole.
FIG. 3 illustrates a cross section of a shaped catalyst prepared as comparative example C3, having dimensions of 5 mmxc3x975mmxc3x972.5 mm (height x diameter x diameter of the central hole).
The novel catalyst shape is also advantageous in the case of supported catalysts which are produced by applying the active components to the preshaped inert support by impregnation with, vapor deposition of or spraying-on of a solution or suspension of the components in the oxidic or salt form.
There are no restrictions in respect of the chemical composition of the catalysts.
The shaped catalysts of the present invention are suitable for heterogeneously catalyzed reactions in which they are used, for example, as fixed beds in gas-phase or liquid-phase reactions, in particular in strongly exothermic gas-phase reactions such as the oxychlorination of ethylene to form 1,2-dichloroethane.
The shaped catalysts of the present invention are preferably used for oxychlorination, in particular of ethylene to 1,2-dichloroethane. The composition of catalysts suitable for oxychlorination is based on a support, which preferably comprises a high-surface-area aluminum oxide such as xcex3- or xcex4-Al2O3. The BET surface area is generally in the range from 100 to 250 m2/g, preferably from 150 to 220 m2/g. Preferably, the support is, in a first step, shaped to the desired catalyst geometry by tableting, and active components are applied to the shape support in a subsequent step. In the starting material used for tableting the support, the high-surface-area aluminum oxide may be replaced completely or partly by other compounds such as pseudoboehmite which can be converted by calcination into a high-surface-area aluminum oxide. In addition, tableting aids such as graphite or magnesium stearate can also be added to the starting material to be tableted. Preference is given to using tableting mixtures as described in WO-A 99/48606.
According to the present invention, the material is tableted to form hollow cylinders or annular tablets. The hollow cylinders or rings generally have an arithmetic mean height of from 3 to 7 mm, preferably from 4.8 to 5.2 mm, particularly preferably from 4.9 to 5.1 mm, an arithmetic mean diameter of from 3 to 7 mm, preferably from 4.8 to 5.2 mm, particularly preferably from 4.9 to 5.1 mm, and an arithmetic mean diameter of the central hole of from 2 to 3.5 mm, preferably from 2.3 to 2.7 mm, particularly preferably from 2.4 to 2.6 mm.
After tableting, the catalyst supports are generally calcined. Calcination is generally carried out at from 500 to 800xc2x0 C., preferably from 700 to 750xc2x0 C. Calcination is generally performed in an oxidizing atmosphere, generally in air.
The tableting process described and the choice of starting materials generally gives a catalyst support which has both a good mechanical stability and a pore volume advantageous for oxychlorination. The catalyst supports for the oxychlorination which are obtained according to the present invention generally have a pore volume of from 0.1 to 0.9 cm3/g, preferably from 0.3 to 0.7 cm3/g, particularly preferably from 0.4 to 0.6 cm3/g and a lateral compressive strength of at least 20 N, preferably from 22 to 80 N, particularly preferably from 25 to 60 N, in particular from 27 to 55 N.
The supports obtained in this way can subsequently be impregnated with a solution of CuCl2 and, if desired, further compounds such as KCl, other salts of alkali metals, alkaline earth metals or rare earth metals. If desired, hydrochloric acid can also be added to such a solution.
The volume of the impregnation solution is advantageously chosen so that it corresponds to from 10 to 200% of the pore volume of the support, preferably from 30 to 150%, particularly preferably from 90 to 110%.
After impregnation, the shaped catalyst bodies are generally dried at from 80 to 300xc2x0 C., preferably from 100 to 200xc2x0 C.
The concentration and the volume of the impregnation solution are chosen so that the supported catalyst generally has a Cu content of from 1 to 15% by weight, preferably from 2 to 10% by weight, and a K content of from 0.1 to 8% by weight, preferably from 0.3 to 3% by weight. The activity profile of the catalyst composition can be set as desired by selection of the metal concentrations in the catalyst and, if desired, by dilution with inert material such as Al2O3. The supported catalyst obtainable in this way is suitable for preparing 1,2-dichloroethane by oxychorination. It combines a low pressure drop with good mechanical strength.
The total pore volume (Hg porosimetry) of the catalyst supports of the present invention is at least 0.35 ml/g, preferably at least 0.4 ml/g, and the proportion of macropores is at least 10%, preferably from 15 to 50%, particularly preferably from 20 to 40%, over the total pore volume.
The novel shaped catalysts are suitable preferably for the oxychlorination of ethylene and, as a rule, also for other heterogeneously catalyzed reactions, for example for the preparation of acrylic acid, phthalic anhydride and maleic anhydride or the dehydrogenation of alkanes to alkenes, for example propane to propene. The preparation of catalysts shaped according to the invention which are intended for such and further reactions can be carried out analogously to the preparation of other catalysts suitable for this reaction, apart from the shaping according to the invention. These catalysts may be supported catalysts or unsupported catalysts.